CN106698860B - Nitrobenzene wastewater treatment process - Google Patents
Nitrobenzene wastewater treatment process Download PDFInfo
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- CN106698860B CN106698860B CN201710128990.0A CN201710128990A CN106698860B CN 106698860 B CN106698860 B CN 106698860B CN 201710128990 A CN201710128990 A CN 201710128990A CN 106698860 B CN106698860 B CN 106698860B
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- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 title claims abstract description 190
- 238000000034 method Methods 0.000 title claims abstract description 73
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 20
- 239000002351 wastewater Substances 0.000 claims abstract description 113
- 238000011282 treatment Methods 0.000 claims abstract description 81
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000003197 catalytic effect Effects 0.000 claims abstract description 16
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000004062 sedimentation Methods 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 7
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 7
- 230000000977 initiatory effect Effects 0.000 claims abstract description 5
- 239000010802 sludge Substances 0.000 claims description 71
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 28
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 21
- 230000014759 maintenance of location Effects 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000010865 sewage Substances 0.000 claims description 15
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 14
- 239000011790 ferrous sulphate Substances 0.000 claims description 14
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 12
- 238000006385 ozonation reaction Methods 0.000 claims description 11
- 239000000706 filtrate Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 235000015097 nutrients Nutrition 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 230000000975 bioactive effect Effects 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910001369 Brass Inorganic materials 0.000 claims description 6
- 229910001018 Cast iron Inorganic materials 0.000 claims description 6
- 239000010951 brass Substances 0.000 claims description 6
- 238000011221 initial treatment Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 4
- 230000005855 radiation Effects 0.000 claims description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 abstract description 8
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 230000000813 microbial effect Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract 2
- 238000001514 detection method Methods 0.000 description 17
- 238000001179 sorption measurement Methods 0.000 description 14
- 238000005273 aeration Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F2003/001—Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms
- C02F2003/003—Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms using activated carbon or the like
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4612—Controlling or monitoring
- C02F2201/46125—Electrical variables
- C02F2201/46135—Voltage
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- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4612—Controlling or monitoring
- C02F2201/4615—Time
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- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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- Treatment Of Water By Oxidation Or Reduction (AREA)
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Abstract
The invention relates to a nitrobenzene wastewater treatment process, which comprises the following steps: (1) treating the wastewater to be treated by adopting an electrolysis reaction to prepare electrolysis-induced wastewater; (2) carrying out biological reduction treatment on the electrolysis-initiated wastewater to prepare a reduction mixed system; (3) carrying out mud-water separation on the reduction mixed system to prepare reduction wastewater; (4) introducing the reduction wastewater into an aerobic biochemical tank, and performing aerobic treatment to prepare an aerobic mixed system; (5) introducing the aerobic mixed system into a secondary sedimentation tank, and performing sludge-water separation to obtain aerobic wastewater; (6) and (3) carrying out catalytic oxidation treatment on the aerobic wastewater by ozone to prepare treated wastewater. The invention excites the nitro active sites on the nitrobenzene molecules through the electrolytic initiation action of high-voltage pulses, then efficiently reduces the nitrobenzene molecules through the subsequent enhanced biological reduction action, converts the nitrobenzene molecules into aniline which is beneficial to microbial degradation, obviously improves the biological adaptability of the wastewater, and creates good conditions for the subsequent biochemical treatment.
Description
Technical Field
The invention relates to a nitrobenzene wastewater treatment process, and belongs to the technical field of industrial wastewater treatment.
Background
Nitrobenzene is an important chemical raw material and a fine chemical intermediate, belongs to highly toxic chemicals and has great harm to the ecological environment, so that the nitrobenzene substances in the wastewater discharge standard of China have strict standards.
The nitrobenzene wastewater has the characteristics of strong biological toxicity, high pollutant concentration, high salt content, high chromaticity and the like, and belongs to typical refractory industrial wastewater.
Nitrobenzene molecules have strong biological toxicity and are difficult to degrade by microorganisms. The method for treating the nitrobenzene wastewater mainly comprises a physical method, a chemical method, a biological method and a combination method of the three methods.
Chinese patent document CN103588314A (application No. 201310569967.7) discloses a process for treating nitrobenzene wastewater by a resin adsorption method, which is characterized in that: the nitrobenzene wastewater is cooled by a cooler and then enters a first adsorption column; adsorbing nitrobenzene in the nitrobenzene wastewater by using the first adsorption column, then introducing the nitrobenzene wastewater into the second adsorption column for re-adsorption, and introducing the finished product wastewater with the nitrobenzene content of less than 0-10 ppm after the two-time adsorption into a finished product wastewater tank; sampling and analyzing at a finished product wastewater sampling point every 8 hours, simultaneously sampling and analyzing at a nitrobenzene wastewater circulating sampling point, and switching a first adsorption column when the first adsorption column is in adsorption saturation; after the switching is completed, the second adsorption column and the third adsorption column are connected in series for use, the adsorption is carried out twice and then the discharge is carried out, and the first adsorption column carries out resin regeneration.
Chinese patent document CN104591377A (application No. 201510047407.4) discloses a method for treating nitrobenzene wastewater by using an ozone biological aerated filter and application thereof, wherein the method comprises the following steps: (1) the method comprises the steps of (1) constructing the biofilter, (2) starting the air aeration biofilter, (3) starting the ozone aeration biofilter, and (4) operating the ozone aeration biofilter. The invention combines ozone zeolite catalytic oxidation and biological oxidation into a whole, utilizes the strong oxidizing property of ozone to open the ring of nitrobenzene, the open-ring nitrobenzene can participate in the co-metabolism degradation of the nitrobenzene as a degradable matrix, the removal effect of the nitrobenzene is improved, the oxidation products are degraded by a biological film growing on the zeolite filler on the upper part of the reactor, and the efficient degradation of the nitrobenzene is realized in the same reactor.
The process removes the nitrobenzene in the wastewater to a certain extent, but the resin adsorption method only transfers the nitrobenzene from the wastewater to other phase states, the analytic solution still needs to be treated, the resin regeneration efficiency is low, and the treatment cost is high; the ozone aeration biological filter method for treating the nitrobenzene wastewater has high treatment cost, and has low nitrobenzene removal efficiency and poor decoloring effect when treating the nitrobenzene production wastewater with high salt content. The removal of nitrobenzene in the wastewater is greatly hindered by the above disadvantages.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the nitrobenzene wastewater treatment process which has high nitrobenzene reduction efficiency, high removal efficiency of pollutants in wastewater, no secondary pollution in the treatment process and low operation cost.
The technical scheme of the invention is as follows:
a nitrobenzene wastewater treatment process comprises the following steps:
(1) carrying out electrolytic reaction treatment on the wastewater to be treated, wherein the hydraulic retention time of the electrolytic reaction is 5-10 min, and the working voltage is 400-450V, so as to prepare electrolytic initiation wastewater;
(2) introducing the electrolysis-induced wastewater prepared in the step (1) into a biological reduction tank, adjusting the pH to 7.0-7.5, adding ferrous sulfate, performing biological reduction treatment, and allowing hydraulic retention time to be 24-36 h to prepare a reduction mixed system;
(3) introducing the reduction mixed system prepared in the step (2) into a primary sedimentation tank, separating mud and water to prepare reduction wastewater and reduction biochemical sludge, and refluxing the reduction biochemical sludge to a biological reduction tank;
(4) introducing the reduction wastewater prepared in the step (3) into an aerobic biochemical tank, and performing aerobic treatment to prepare an aerobic mixed system;
(5) introducing the aerobic mixed system prepared in the step (4) into a secondary sedimentation tank, separating mud and water to prepare aerobic wastewater and aerobic biochemical sludge, and refluxing the aerobic biochemical sludge to the aerobic biochemical tank;
(6) and (4) carrying out catalytic ozonation treatment on the aerobic wastewater prepared in the step (5) to prepare treated wastewater.
According to the invention, the wastewater to be treated in the step (1) is preferably nitrobenzene wastewater with the pH value adjusted to 5.0-5.5.
Preferably, the power supply for the electrolytic reaction in the step (1) is a high-voltage pulse direct current power supply, the anode plate is made of cast iron, and the cathode plate is made of brass.
According to the invention, the concentration of the sludge subjected to biological reduction treatment in the step (2) is preferably 5000mg/L to 8000 mg/L; preferably, the biological reduction pond sludge is inoculated with the strain BioRemove 5150 and the activated sludge of the municipal sewage treatment plant at the initial culture stage; the strain BioRemove 5150 is available from Novovern, Denmark.
According to the invention, the adding amount of the ferrous sulfate in the step (2) is preferably 5-10 mg/L calculated by ferrous sulfate heptahydrate.
Preferably, in the step (4), the aerobic treatment is a treatment by a PACT process;
further preferably, the PACT process conditions are as follows: under the conditions that the dissolved oxygen is 2.0-3.0 mg/L and the sludge concentration is 6000-8000 mg/L, the hydraulic retention time is 36-48 h; the strain BioRemove 5150 and the activated sludge of the municipal sewage treatment plant are inoculated in the initial treatment stage of the PACT process. The strain BioRemove 5150 is available from Novovern, Denmark.
Preferably, in the PACT process, the adding amount of the powdered activated carbon is 10-20 mg/L, the adding amount of the organic nutrient is 20-40 mg/L, and the adding amount of the bioactive phosphorus is 5-10 mg/L; more preferably, the powdered activated carbon is shell-based activated carbon with the particle size of 100 meshes. The shell-based activated carbon having a particle size of 100 mesh is a common commercially available product.
The organic nutrient can be prepared by adopting common commercial products or the method described in Chinese patent document CN103224887A (application No. 201310164864.2) specification examples 1-3; the bioactive phosphorus can be prepared by common commercial products or Chinese patent document CN101560117A (application number 200810041764. X).
According to the invention, in the step (6), the adding amount of the ozone for the catalytic ozonation treatment is 20-30 mg/L, and the strength is 180-220 μ w/cm2The ultraviolet radiation is carried out for 20-30 min.
According to the invention, the method also comprises the step of mixing the dehydrated filtrate with the wastewater to be treated in the step (1) after dehydrating the reduced biochemical sludge prepared in the step (3) and the aerobic biochemical sludge prepared in the step (5).
Advantageous effects
1. The invention organically combines 'electrolysis initiation' and 'enhanced biological reduction', excites the nitro active sites on nitrobenzene molecules through the electrolysis initiation effect of high-voltage pulse, then efficiently reduces the nitrobenzene molecules through the subsequent enhanced biological reduction effect, converts the nitrobenzene molecules into aniline beneficial to microbial degradation, has the nitrobenzene reduction rate of over 98 percent, obviously improves the biological adaptability of the waste water, creates good conditions for the subsequent biochemical treatment, and saves the electricity consumption and the polar plate consumption of the electrolysis treatment process by over 80 percent compared with the conventional treatment method;
2. the aerobic biochemical treatment adopts a PACT treatment process, and a high-efficiency microbial degradation system with strong impact resistance is formed through the processes of inoculation and domestication of high-efficiency microorganisms, directional culture of nutrient substances, fixation of activated carbon carriers and the like, so that the aim of efficiently removing aniline pollutants in wastewater is fulfilled, and the removal rate of COD is up to more than 95%;
3. according to the invention, the ultraviolet light catalytic ozone oxidation advanced treatment section is arranged after biochemical treatment, aiming at pollutants which cannot be removed by front-end biochemical treatment, organic pollutants and chromophoric groups in wastewater are further efficiently removed through ultraviolet light catalytic ozone oxidation, the effluent quality is improved, the treatment process has ideal decolorization efficiency, no waste gas or waste residue is generated in the treatment process, and the process is environment-friendly;
4. aiming at the water quality characteristics of the nitrobenzene wastewater, the invention realizes the process effects of good treatment effect, low treatment cost and convenient operation and management by organically combining the processes of physical and chemical treatment, biochemical treatment and physical and chemical treatment, achieves the high-efficiency removal of pollutant indexes such as nitrobenzene, COD (chemical oxygen demand), chromaticity and the like in the wastewater, and has the remarkable characteristics of economy, high efficiency and environmental protection.
Detailed Description
The technical solution of the present invention is further described with reference to the following examples, but the scope of the present invention is not limited thereto.
Sources of materials
The strain BioRemove 5150 described in the examples, available from Novedule, Denmark;
in the embodiment, the activated sludge of the municipal sewage treatment plant is from a local municipal sewage treatment plant;
the organic nutrient is prepared by the method described in example 1 in Chinese patent document CN 103224887A;
the bioactive phosphorus described in the examples was prepared according to the method described in example 1 of chinese patent document CN 101560117A.
In the embodiment, the powdered activated carbon is ordinary commercially available shell-based activated carbon with the particle size of 100 meshes, which is available from environmental science and technology limited of national academy of sciences in Shandong province;
detection method
CODCrGB11914-89 is adopted for detection, HJ592-2010 is adopted for nitrobenzene detection, GB6920-1986 is adopted for pH detection, and GB/T11903-.
Example 1
Nitrobenzene wastewater of a certain Nitrobenzene production enterprise in eastern Shandong has the indexes of: CODCr1685mg/L, 148mg/L nitrobenzene, pH 7.6, and 600 times of color.
A nitrobenzene wastewater treatment process comprises the following steps:
(1) adjusting the pH value of nitrobenzene wastewater to 5.0 to prepare wastewater to be treated, and then treating the wastewater to be treated by an electrolytic reaction, wherein the hydraulic retention time of the electrolytic reaction is 10min, and the working voltage is 450V to prepare electrolysis-initiated wastewater;
the power supply for the electrolytic reaction adopts a high-voltage pulse direct-current power supply, the anode plate is made of cast iron, and the cathode plate is made of brass;
(2) introducing the electrolysis-induced wastewater prepared in the step (1) into a biological reduction tank, adjusting the pH to 7.5, adding ferrous sulfate, wherein the adding amount of the ferrous sulfate is 10mg/L calculated by ferrous sulfate heptahydrate, performing biological reduction treatment, and keeping the hydraulic retention time for 36 hours to prepare a reduction mixed system;
the concentration of the sludge subjected to biological reduction treatment is 8000 mg/L; inoculating a strain BioRemove 5150 and activated sludge of a municipal sewage treatment plant to the sludge of the biological reduction tank at the initial culture stage;
through detection, CODCr1525mg/L of Mirabilitum2.1mg/L of phenyl, 7.2 pH and 240 times of chroma.
(3) Introducing the reduction mixed system prepared in the step (2) into a primary sedimentation tank, separating mud and water to prepare reduction wastewater and reduction biochemical sludge, dehydrating the reduction biochemical sludge, mixing dehydrated filtrate with the wastewater to be treated in the step (1), and refluxing the dehydrated reduction biochemical sludge to a biological reduction tank;
(4) introducing the reduction wastewater prepared in the step (3) into an aerobic biochemical tank, and treating by using a PACT (packet aeration treatment) process to prepare an aerobic mixed system;
the PACT process treatment conditions are as follows: under the conditions that the dissolved oxygen is 3.0mg/L and the sludge concentration is 8000mg/L, the hydraulic retention time is 48 h; inoculating a strain BioRemove 5150 and activated sludge of a municipal sewage treatment plant at the initial treatment stage of the PACT process;
in the PACT process, the adding amount of powdered activated carbon is 20mg/L, the adding amount of organic nutrient is 40mg/L, and the adding amount of bioactive phosphorus is 10 mg/L;
through detection, CODCr96mg/L, nitrobenzene 0.2mg/L, pH 7.1, and color 80 times.
(5) Introducing the aerobic mixed system prepared in the step (4) into a secondary sedimentation tank, separating mud and water to prepare aerobic wastewater and aerobic biochemical sludge, dehydrating the aerobic biochemical sludge, mixing a dehydration filtrate with the wastewater to be treated in the step (1), and refluxing the dehydrated aerobic biochemical sludge to the aerobic biochemical tank;
(6) carrying out catalytic ozonation treatment on the aerobic wastewater prepared in the step (5), wherein the addition amount of ozone for the catalytic ozonation treatment is 30mg/L, and the strength is 200 mu w/cm2Irradiating for 30min to obtain the treated wastewater.
Through detection, CODCr78mg/L, nitrobenzene 0.2mg/L, pH 7.1, color 20 times.
Example 2
The nitrobenzene wastewater treatment process as in example 1, except that the electrolytic reaction hydraulic retention time in step (1) was 5min and the operating voltage was 420V.
The reduction mixed system is detected to be CODCr1570mg/L, nitrobenzene 2.9mg/L, pH 7.2, color 280 times.
The treated wastewater is detected as CODCr88mg/L, nitrobenzene 0.4mg/L, pH 7.2, color 30 times.
Example 3
The nitrobenzene wastewater treatment process as in example 1, except that in step (2), pH is adjusted to 7.0, ferrous sulfate is added, the amount of ferrous sulfate added is 5mg/L based on ferrous sulfate heptahydrate, biological reduction treatment is performed, and the hydraulic retention time is 24 hours, so as to prepare a reduction mixed system;
the concentration of the sludge subjected to biological reduction treatment is 6000 mg/L; inoculating a strain BioRemove 5150 and activated sludge of a municipal sewage treatment plant to the sludge of the biological reduction tank at the initial culture stage;
the reduction mixed system is detected to be CODCr1583mg/L, nitrobenzene 2.7mg/L, pH 7.2, color 280 times.
The treated wastewater is detected as CODCr85mg/L, 0.35mg/L nitrobenzene, pH 7.2 and chroma 30 times.
Example 4
The nitrobenzene wastewater treatment process as described in example 1, except that the reduced wastewater in step (4) is introduced into an aerobic biochemical tank by using the conventional activated sludge process.
The aerobic mixed system is detected to be CODCr345mg/L, nitrobenzene 1.7mg/L, pH 7.2 and color 160 times.
The treated wastewater is detected as CODCr325mg/L, nitrobenzene 1.6mg/L, pH 7.2, color 90 times.
Comparative example 1
The nitrobenzene wastewater described in example 1 was treated according to the procedure described in example 1 of chinese patent document CN104591377A (application No. 201510047407.4) with the following treatment results:
CODCr386mg/L, 8.9mg/L nitrobenzene, 7.4 pH and 100 times chroma.
Example 5
Nitrobenzene wastewater of an enterprise co-producing aniline from certain Nitrobenzene in Shandong lotus leaf has the indexes of: CODCr865mg/L, nitrobenzene 76mg/L, pH 7.8, and color 450 times.
A nitrobenzene wastewater treatment process comprises the following steps:
(1) adjusting the pH value of nitrobenzene wastewater to 5.3 to prepare wastewater to be treated, and then treating the wastewater to be treated by an electrolytic reaction, wherein the hydraulic retention time of the electrolytic reaction is 5min, and the working voltage is 400V to prepare electrolysis-initiated wastewater;
the power supply for the electrolytic reaction adopts a high-voltage pulse direct-current power supply, the anode plate is made of cast iron, and the cathode plate is made of brass;
(2) introducing the electrolysis-induced wastewater prepared in the step (1) into a biological reduction tank, adjusting the pH to 7.5, adding ferrous sulfate, wherein the adding amount of the ferrous sulfate is 5mg/L calculated by ferrous sulfate heptahydrate, performing biological reduction treatment, and keeping the hydraulic retention time for 24 hours to prepare a reduction mixed system;
the concentration of the sludge subjected to biological reduction treatment is 6000 mg/L; inoculating a strain BioRemove 5150 and activated sludge of a municipal sewage treatment plant to the sludge of the biological reduction tank at the initial culture stage;
through detection, CODCr782mg/L, nitrobenzene 1.2mg/L, pH 7.4, and color 200 times.
(3) Introducing the reduction mixed system prepared in the step (2) into a primary sedimentation tank, separating mud and water to prepare reduction wastewater and reduction biochemical sludge, dehydrating the reduction biochemical sludge, mixing dehydrated filtrate with the wastewater to be treated in the step (1), and refluxing the dehydrated reduction biochemical sludge to a biological reduction tank;
(4) introducing the reduction wastewater prepared in the step (3) into an aerobic biochemical tank, and treating by using a PACT (packet aeration treatment) process to prepare an aerobic mixed system;
the PACT process treatment conditions are as follows: under the conditions that the dissolved oxygen is 2.0mg/L and the sludge concentration is 6000mg/L, the hydraulic retention time is 36 h; inoculating a strain BioRemove 5150 and activated sludge of a municipal sewage treatment plant at the initial treatment stage of the PACT process;
in the PACT process, the adding amount of powdered activated carbon is 15mg/L, the adding amount of organic nutrient is 20mg/L, and the adding amount of bioactive phosphorus is 5 mg/L;
through detection, CODCr60mg/L, 0.1mg/L nitrobenzene, pH 7.3 and color 40 times.
(5) Introducing the aerobic mixed system prepared in the step (4) into a secondary sedimentation tank, separating mud and water to prepare aerobic wastewater and aerobic biochemical sludge, dehydrating the aerobic biochemical sludge, mixing a dehydration filtrate with the wastewater to be treated in the step (1), and refluxing the dehydrated aerobic biochemical sludge to the aerobic biochemical tank;
(6) carrying out catalytic ozonation treatment on the aerobic wastewater prepared in the step (5), wherein the adding amount of ozone for the catalytic ozonation treatment is 25mg/L, and the strength is 180 mu w/cm2Irradiating for 20min to obtain the treated wastewater.
Through detection, CODCr45mg/L, nitrobenzene 0.1mg/L, pH 7.3, color 10 times.
Comparative example 2
The nitrobenzene wastewater described in example 5 was treated according to the procedure described in example 2 of chinese patent document CN104591377A (application No. 201510047407.4) with the following treatment results:
CODCr147mg/L, 5.6mg/L nitrobenzene, pH 7.1 and 80 times chroma.
Comparative example 3
The nitrobenzene wastewater treatment process as described in example 1, except that the electrolytic reaction hydraulic retention time in step (1) was 15min and the operating voltage was 350V.
The reduction mixed system is detected to be CODCr1595mg/L, nitrobenzene 4.7mg/L, pH 7.2, and color 260 times.
The treated wastewater is detected as CODCr116mg/L, nitrobenzene 0.4mg/L, pH 7.2, color 30 times.
Comparative example 4
The nitrobenzene wastewater treatment process as in example 1, except that the steps are as follows:
(1) introducing the nitrobenzene wastewater into a biological reduction tank, adjusting the pH value to 7.5, adding ferrous sulfate, wherein the adding amount of the ferrous sulfate is 5mg/L calculated by ferrous sulfate heptahydrate, performing biological reduction treatment, and keeping the hydraulic retention time for 24 hours to prepare a reduction mixed system;
the concentration of the sludge subjected to biological reduction treatment is 6000 mg/L; inoculating a strain BioRemove 5150 and activated sludge of a municipal sewage treatment plant to the sludge of the biological reduction tank at the initial culture stage; CODCr1685mg/L, 148mg/L nitrobenzene, pH 7.6, and 600 times of color.
Through detection, CODCr1610mg/L, nitrobenzene 26.6mg/L, pH 7.2, and color 300 times.
(2) Introducing the reduction mixed system prepared in the step (1) into a primary sedimentation tank, separating mud and water to prepare reduction wastewater and reduction biochemical sludge, dehydrating the reduction biochemical sludge, mixing the dehydrated filtrate with wastewater to be treated, and refluxing the dehydrated reduction biochemical sludge to a biological reduction tank;
(3) introducing the reduction wastewater prepared in the step (2) into an aerobic biochemical tank, and treating by using a PACT (packet aeration treatment) process to prepare an aerobic mixed system;
the PACT process treatment conditions are as follows: under the conditions that the dissolved oxygen is 2.0mg/L and the sludge concentration is 6000mg/L, the hydraulic retention time is 36 h; inoculating a strain BioRemove 5150 and activated sludge of a municipal sewage treatment plant at the initial treatment stage of the PACT process;
in the PACT process, the adding amount of powdered activated carbon is 15mg/L, the adding amount of organic nutrient is 20mg/L, and the adding amount of bioactive phosphorus is 5 mg/L;
through detection, CODCr295mg/L, 4.2mg/L nitrobenzene, pH 7.2 and 150 times chroma.
(4) Introducing the aerobic mixed system prepared in the step (3) into a secondary sedimentation tank, separating mud and water to prepare aerobic wastewater and aerobic biochemical sludge, dehydrating the aerobic biochemical sludge, mixing a dehydration filtrate with the wastewater to be treated in the step (1), and refluxing the dehydrated aerobic biochemical sludge to the aerobic biochemical tank;
(5) adjusting the pH value of the aerobic wastewater to 5.3 to prepare wastewater to be treated, and then treating the wastewater to be treated by an electrolytic reaction, wherein the hydraulic retention time of the electrolytic reaction is 5min, and the working voltage is 400V to prepare electrolysis-initiated wastewater;
the power supply for the electrolytic reaction adopts a high-voltage pulse direct-current power supply, the anode plate is made of cast iron, and the cathode plate is made of brass;
(6) carrying out catalytic ozonation treatment on the electrolysis-initiated wastewater prepared in the step (5), wherein the addition amount of ozone for the catalytic ozonation treatment is 25mg/L, and the strength is 200 mu w/cm2Ultraviolet radiation ofAnd (5) 20min to obtain the treated wastewater.
Through detection, CODCr268mg/L, nitrobenzene 3.9mg/L, pH 7.2, color 80 times.
Example 6
The nitrobenzene wastewater of a certain nitrobenzene production enterprise of Jiangsu Xiangshui has the indexes of: CODCr960mg/L, 89mg/L nitrobenzene, pH 7.9, color 500 times.
A nitrobenzene wastewater treatment process comprises the following steps:
(1) adjusting the pH value of nitrobenzene wastewater to 5.0 to prepare wastewater to be treated, and then treating the wastewater to be treated by an electrolytic reaction, wherein the hydraulic retention time of the electrolytic reaction is 8min, and the working voltage is 420V to prepare electrolysis-initiated wastewater;
the power supply for the electrolytic reaction adopts a high-voltage pulse direct-current power supply, the anode plate is made of cast iron, and the cathode plate is made of brass;
(2) introducing the electrolysis-induced wastewater prepared in the step (1) into a biological reduction tank, adjusting the pH value to 7.3, adding ferrous sulfate, wherein the adding amount of the ferrous sulfate is 8mg/L calculated by ferrous sulfate heptahydrate, performing biological reduction treatment, and keeping the hydraulic retention time for 32 hours to prepare a reduction mixed system;
the concentration of the sludge subjected to biological reduction treatment is 7000 mg/L; inoculating a strain BioRemove 5150 and activated sludge of a municipal sewage treatment plant to the sludge of the biological reduction tank at the initial culture stage;
through detection, CODCr865mg/L, nitrobenzene 1.6mg/L, pH 7.4, and color 250 times.
(3) Introducing the reduction mixed system prepared in the step (2) into a primary sedimentation tank, separating mud and water to prepare reduction wastewater and reduction biochemical sludge, dehydrating the reduction biochemical sludge, mixing dehydrated filtrate with the wastewater to be treated in the step (1), and refluxing the dehydrated reduction biochemical sludge to a biological reduction tank;
(4) introducing the reduction wastewater prepared in the step (3) into an aerobic biochemical tank, and treating by using a PACT (packet aeration treatment) process to prepare an aerobic mixed system;
the PACT process treatment conditions are as follows: under the conditions that the dissolved oxygen is 3.0mg/L and the sludge concentration is 8000mg/L, the hydraulic retention time is 42 h; inoculating a strain BioRemove 5150 and activated sludge of a municipal sewage treatment plant at the initial treatment stage of the PACT process;
in the PACT process, the adding amount of powdered activated carbon is 15mg/L, the adding amount of organic nutrient is 30mg/L, and the adding amount of bioactive phosphorus is 8 mg/L;
through detection, CODCr81mg/L, nitrobenzene 0.18mg/L, pH 7.4, color 80 times.
(5) Introducing the aerobic mixed system prepared in the step (4) into a secondary sedimentation tank, separating mud and water to prepare aerobic wastewater and aerobic biochemical sludge, dehydrating the aerobic biochemical sludge, mixing a dehydration filtrate with the wastewater to be treated in the step (1), and refluxing the dehydrated aerobic biochemical sludge to the aerobic biochemical tank;
(6) carrying out catalytic ozonation treatment on the aerobic wastewater prepared in the step (5), wherein the addition amount of ozone for the catalytic ozonation treatment is 30mg/L, and the strength is 220 mu w/cm2Irradiating for 25min by ultraviolet rays to obtain the treated wastewater.
Through detection, CODCr56mg/L, nitrobenzene 0.15mg/L, pH 7.4, color 20 times.
Comparative example 5
The nitrobenzene wastewater in example 6 was treated according to the procedure described in example 3 of chinese patent document CN104591377A (application No. 201510047407.4).
Through detection, CODCr176mg/L, nitrobenzene 6.4mg/L, pH 7.1, color 80 times.
Claims (5)
1. A nitrobenzene wastewater treatment process is characterized by comprising the following steps:
(1) carrying out electrolytic reaction treatment on the wastewater to be treated, wherein the hydraulic retention time of the electrolytic reaction is 5-10 min, and the working voltage is 400-450V, so as to prepare electrolytic initiation wastewater;
the wastewater to be treated is nitrobenzene wastewater with the pH value adjusted to 5.0-5.5;
the power supply for the electrolytic reaction adopts a high-voltage pulse direct-current power supply, the anode plate is made of cast iron, and the cathode plate is made of brass;
(2) introducing the electrolysis-induced wastewater prepared in the step (1) into a biological reduction tank, adjusting the pH to 7.0-7.5, adding ferrous sulfate, performing biological reduction treatment, and allowing hydraulic retention time to be 24-36 h to prepare a reduction mixed system;
the dosage of the ferrous sulfate is 5-10 mg/L calculated by ferrous sulfate heptahydrate;
the concentration of the sludge subjected to biological reduction treatment is 5000-8000 mg/L;
(3) introducing the reduction mixed system prepared in the step (2) into a primary sedimentation tank, separating mud and water to prepare reduction wastewater and reduction biochemical sludge, and refluxing the reduction biochemical sludge to a biological reduction tank;
(4) introducing the reduction wastewater prepared in the step (3) into an aerobic biochemical tank, and performing aerobic treatment to prepare an aerobic mixed system;
in the step (4), the aerobic treatment is carried out by adopting a PACT process, and the PACT process treatment conditions are as follows: under the conditions that the dissolved oxygen is 2.0-3.0 mg/L and the sludge concentration is 6000-8000 mg/L, the hydraulic retention time is 36-48 h; inoculating a strain BioRemove 5150 and activated sludge of a municipal sewage treatment plant at the initial treatment stage of the PACT process;
in the PACT process, the adding amount of powdered activated carbon is 10-20 mg/L, the adding amount of organic nutrient is 20-40 mg/L, and the adding amount of bioactive phosphorus is 5-10 mg/L;
(5) introducing the aerobic mixed system prepared in the step (4) into a secondary sedimentation tank, separating mud and water to prepare aerobic wastewater and aerobic biochemical sludge, and refluxing the aerobic biochemical sludge to the aerobic biochemical tank;
(6) and (4) carrying out catalytic ozonation treatment on the aerobic wastewater prepared in the step (5) to prepare treated wastewater.
2. The nitrobenzene wastewater treatment process according to claim 1, wherein the bioreduction pond sludge in step (2) is inoculated with the strain BioRemove 5150 and the municipal sewage treatment plant activated sludge at the initial stage of the culture.
3. The nitrobenzene wastewater treatment process according to claim 1, wherein the powdered activated carbon is nutshell-based activated carbon having a particle size of 100 mesh.
4. The nitrobenzene wastewater treatment process according to claim 1, wherein in the step (6), the ozone adding amount of the catalytic ozone oxidation treatment is 20-30 mg/L, and the intensity is 180-220 μ w/cm2The ultraviolet radiation is carried out for 20-30 min.
5. The nitrobenzene wastewater treatment process according to claim 1, further comprising the step of mixing the dehydrated filtrate with the wastewater to be treated in step (1) after dehydrating the reduced biochemical sludge produced in step (3) and the aerobic biochemical sludge produced in step (5).
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| CN1644529A (en) * | 2004-12-22 | 2005-07-27 | 中国石化集团南京化学工业有限公司 | Fully biological treatment of wastewater of nitrobenzol or aniline or their mixture |
| CN101279808A (en) * | 2008-05-28 | 2008-10-08 | 北京大学 | Method for processing nitrobenzene and aniline waste water |
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| CN101279808A (en) * | 2008-05-28 | 2008-10-08 | 北京大学 | Method for processing nitrobenzene and aniline waste water |
| WO2012055101A1 (en) * | 2010-10-27 | 2012-05-03 | Peking University | Treatment system and method for treating waste product |
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